Dual astringent composition

ABSTRACT

Aerosol astringent package having both immediate and continuing effectiveness and comprising in a pressure resistant dispensing container, ethanol, a liquefied propellant and first and second astringents, one alcohol soluble, the other alcohol insoluble. The potentially corrosive effect of the alcohol soluble astringent is limited by mixing sufficient propellant with the ethanol to keep the soluble astringent out of solution, inactive and noncorrosive. Upon dispensing, the loss of propellant from the product enables alcohol solution and activation of the first astringent, for immediate astringent effectiveness. The loss of alcohol from the deposited product and water contact with the second astringent activates the second astringent providing continuing effectiveness.

Unlted States Patent 1191 1111 3,863,005

Mace et al. 1 Jan. 28, 1975 DUAL ASTRINGENT COMPOSITION [75] lnventors' Harry W Mace, Milford Fred Primary E'mmi'ler smnley Assistant Examiner-Dale R. re

Presam' Fan-field both of Conn' Attorney, Agent, or Firm-Louis .I. Bachand [73] Assignee: Aerosol Techniques Incorporated,

Milford, Conn. [57] ABSTRACT 22 Filed: Mar. 5, 1970 I I Aerosol astrmgent package havmg both 1mmcd1atc PP 161764 and continuing effectiveness and comprising in a pressure resistant dispensing container. ethanoL a lique- 521 US. Cl 424/45, 424/47, 424/68 fled propellant and r an sedmd astringents, 6116 51 1m. 01. A6ll 9/04, A6lk 7/00 alcohol Soluble the other alcohol insoluble- The 58 Field 61 Search 424/68, 47, 45 tehtiahy corrosive effect of the alcohol Soluble gent is limited by mixing sufficient propellant with the [56] References Cited ethanol to keep the soluble astringent out of solution, inactive and noncorrosive. Upon dispensing, the loss UNITED STATES PATENTS of propellant from the product enables alcohol solu- 3,823.l69 2/1958 Brown. Jr. et al. 424/68 tion and activation of the first astringent for immedi g' gg ate astringent effectiveness. The loss of alcohol from 3420932 M969 1021 g 424/47 the deposited product and water contact with the sec- 3'472'928 10/1969 424/47 0nd astringent activates the second astringent provid- 3,472,929 10/1969 Jones Et al. 424/68 ihg comihumg effectlvehesi 3,509,253 4/1970 Babbin 424/47 6 Cl 1 D F,

3.714.346 1/1973 Gubernick Cl al. 424/68 DUAL ASTRINGENT COM POSITION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention has to do with antiperspirants. Antiperspirants are personal cosmetics which are applied to the skin and which through astringent action closing or limiting opening of the pores, limits or prevents secretion of perspiration, particularly in underarm areas. Astringency is provided by an astringent such as a halide salt of a multivalent cation particularly aluminum halides.

2. Prior Art Application of astringent salts, which are normally solid, has been effected by spraying a solution thereof in an alcohol based liquid from a plastic squeeze bottle or by propellant powered discharge from an aerosol container. In the latter, the metal container has been subject to corrosion and the valve to clogging, if the astringent salt is in solution in the container. This has been overcome by packaging only propellant and a powdered salt, but new problems of excessive dusting or flyaway and awkward placement arose. Valve clogging may be obviated and dusting lowered, but not eliminated by coating the powdered astringent with an oily liquid, e.g., isopropyl myristate, as has long been known in the art. Amounts of oils effective to reduce dusting. however, may so coat the astringent salt particles as to substantially prolong the period between application and effectiveness, for these salts are effective only when in the ionic, i.e., solution form as will result from contact with body moisture, e.g., secreted perspiration. Moreover, the salts may compact at the container bottom becoming nondispersible and undeliverable in the absence of particulate dispersants such as fine silica. Silica has no astringent function, but replaces deliverable amounts of the astringent salt from the package.

Solution of the astringent salt in the container provides immediate astringent effectiveness on application, but the solution products are corrosive to metal so that the form of antiperspirant product can only be packaged in a plastic squeeze bottle which is an inferior applicator, a specially lined metal aerosol container or plastic coated aerosol glass bottle which are unduly expensive.

BRIEF SUMMARY OF THE INVENTION It is a major objective of the invention to provide an aerosol astringent package overcoming the disadvantages of previously known packages. More specifically, the invention enables the achieving of these objectives:

1. An aerosol dispensible astringent which is immediately effective on application;

2. An aerosol dispersible astringent which has continuing effectiveness responsive to secretion of moisture by the protected body area pores;

3. An astringent composition packageable in ordinary metal aerosol containers, without special, chemically resistant liners;

4. An astringent composition affording the benefits of immediate astringency of an alcohol soluble astringent material and the absence of corrosive attack in ordinary metal aerosol containers;

5. An astringent composition which is undissolved and inactive in the aerosol container but automatically dissolved and activated in passage from the container to the skin surface;

6. An astringent composition in which the maintain ing dispersed of water soluble astringent powder for facile dispensing from an aerosol container is effected by an astringent material, not by large quantities of an inert powder such as silica, or of a suspending liquid such as isopropyl myristate, so that levels of astringently active materials in the package may be higher than previously available astringent aerosol packages;

7. An astringent composition in which propellant is mixed with ethanol in proportions preventing solution of alcohol soluble astringent in the ethanol to maintain this astringent material as a particulate solid capable of acting as an astringently functional dispersing agent for other, nonalcohol soluble astringent in the composition;

8. An aerosol astringent package in which flyaway is limited by the alcohol suspension of the astringent so that emollients such as isopropyl myristate may be used in quite limited amounts, sufficient only for cosmetic elegance, i.e., to form on application a smooth nongreasy film that will not powder.

The foregoing objectives are realized by an aerosol astringent package according to the invention which comprises a pressure resistant container having a dispensing means and under pressure therein an astringent composition providing both immediate and continuing astringent effectiveness when applied, the composition per one hundred parts by weight consisting essentially of a solution of ethanol and from 4 to 30 parts of a normally gaseous liquefied propellant per part of ethanol, at least 0.5 part of a first astringent soluble and highly astringent in alcohol but insoluble in the ethanol propellant solution, the first astringent consisting of aluminum chlorhydroxide-propylene glycol adduct, at least 0.5 part of a second astringent soluble and highly as tringent in water solution but insoluble in ethanol, the second astringent consisting of aluminum chlorhydroxide, the sum of the first and second astringents being between one and twelve parts, to effect, upon dispensing of the composition from the container, alcohol solution and activation of the first astringent as the propellant volatilizes for immediate astringent effectiveness and to effect water solution and activation of the second astringent in the applied condition as the ethanol evaporates and the second astringent is contacted with body moisture, for continuing astringent effectiveness.

DESCRIPTION OF THE PREFERRED EMBODIMENTS It will be noted from the foregoing that the aerosol astringent invention herein described employs an alcohol soluble astringent salt composition or adduct, but

insolubilizes the composition until delivery from the package. Insolubilization is effected by the use of relatively great quantities of propellant with respect to alcohol used.

While the particular alcohol used is not narrowly critical, for practical purposes, a denatured ethanol is the alcohol of choice. The ethanol may be replaced with equivalent amounts of other organic solvents for the alcohol soluble astringent component, e.g., methanol, n-propanol, isopropanol and the like. Typically no more than 25 percent by weight of the ethanol will be so replaced and preferably only ethanol and up to 5 percent by weight a denaturant therefor are used.

The propellant is a normally gaseous compound or mixture of compounds which can be liquefied at conventional aerosol dispenser pressures, e.g., at up to 75 pounds per square inch pressure. Because the aluminum salts employed in the invention contain Karl Fischer Assay detectable water, the resistance of a propellant to hydrolysis, i.e., decomposition in the presence of water will be a factor considered in propellant selection. Among suitable propellants are non-toxic chemically inert materials gaseous at 25C and 760 mm. Hg. pressure and liquefiable at pressures less than about 75 psig. such as alkanes and halogenated alkanes, particularly perhalogenated alkanes, e.g., the Freons (Trademark of duPont). Specific suitable halogenated propellants are the perhalogenated alkanes having 1 to 6 carbon atoms, e.g., dichlorodifluoromethane (Freon 12), dichlorotetrafluoroethane (Freon 1 l4), pentafluoromonochloroethane (Freon 115), perhalogenated cycloalkanes having 4 to 6 carbon atoms, e.g., octafluoropropane (Freon C 218) cyclic hexafluorodichlorobutane (Freon C 316), cyclic octafluorobutane (Freon C 318) and normally gaseous alkanes of 3 to 5 carbon atoms, i.e., propane, butane, isobutane and pentane. Mixtures of those propellants may be used. Preferably the propellant contains at least a major weight proportion of a perhalogenated alkane of from 1 to 2 carbon atoms and no more than 30 weight percent ofa second propellant selected from the above mentioned gaseous alkanes and chloro and fluoro-substituted nonperhalogenated gaseous alkanes, above mentioned.

The present compositions employ relatively large amounts of propellant for the amount of alcohol used. Thus, at least 4 parts by weight of propellant per part of ethanol is used. Preferably the composition contains per 100 parts by weight from 10 to parts of alcohol and conversely 85 to 60 parts of propellant, with the balance being astringent materials and additives. It has been found, that by admixing and dissolving propellant in the alcohol in the mentioned ratios, the alcohol soluble aluminum salt is insolubilized in the composition despite the presence of, e.g., ethanol. That is, the salt is soluble in ethanol per se, but not in intimate mixtures or cosolution of ethanol with more than 4, e.g., with from 4 to 30 and preferably 4 to 12 parts by weight of propellant. The salt may be considered to be precipitated from the ethanol by the addition of the propellant in the quanities mentioned.

The present composition contains as a first astringent effective in alcohol solution but insoluble and ineffective in the ethanol propellant solution at least one-half part per 100 parts of the composition of an adduct of aluminum chlorhydroxide and propylene glycol. Such adducts are described and claimed as aluminum containing coordination compounds or complexes in U.S. Pat. No. 3,420,932 issued Jan. 7, 1969, to Jones and Rubino. This patent is hereby incorporated by reference in this disclosure. The adduct of aluminum chlorhydroxide and propylene glycol is a species of that group of adducts complexes or coordination compounds of uncertain structure having the generalized formula 2 )yz -UH: h.

wherein A is selected from anions of the class of chloride, bromide, iodide, sulfate and sulfamate; R 15 the coordinating moiety of a polyhydroxy compound having a carbon chain in which at least two carbon atoms link a hydroxyl group to said chain; it is a positive integer of from 1 to 4; .r is the valence of A; is a number having a value of from about 0.5 to 6 and is such that (y-z) is not negative in value; and z is the number of available coordination sites, with the product of n and z being from 2 to 4 inclusive. The propylene glycol adducts preferably are of the formula 2 2 0.71.l )4.95.l 0.9-1.l (112 P py in which the propylene glycol may be present in the adduct or complex in one or more of a number of ways. namely with both carbinol hydrogen atoms being lost by condensation or neutralization, or with only one carbinol hydrogen atom being lost by condensation or neutralization, or with both hydroxy groups remaining intact and coordinated and/or chelated to one of the aluminum atoms.

These adducts or complexes may be prepared by combining the appropriate precursor aluminum salt such as an aluminum basic chloride (Al- (OH),Cl,,; in which x is a positive integer of from 2 to S; y is a positive integer of from 1 to 4; and x and y will always total 6 and a suitable polyhydroxy compound such as propylene glycol, 1,1,1-trimethylol propane; 1,3-butylene glycol; glycerine; 2-methyl-2,4-pentane diol, neopcntyl glycol; polyethylene glycol; p-xylene diol; polyepichlorohydrin; butyne-l ,4-diol; 2-ethyl-l ,3-hexanediol; and poly-propylene glycol.

The aluminum chlorhydroxide 1.2-propylene glycol adduct may be prepared by reacting in aqueous media at 43-50 percent solids aluminum chlorohydroxide (e.g., Chlorohydrol, a 5/6 basic aluminum salt having Al and Cl in an atomic ratio of 2:1) having the formula [A1 (OH) Cl],, and from 53 to 100 percent by weight based on the aluminum chlorhydroxide solids content in the aqueous medium of 1,2-propylene glycol and heating at 50 to 120C for a few minutes to several hours depending on temperature and the use or not of stirring. The reaction product is spray dried or vacuum dried to a dry appearing powdery product containing an average from 1 to 10 percent moisture by Karl Fischer Assay.

The solubility characteristics of this type of adduct are given in the aforementioned patent for a specific adduct prepared as above and containing Al 19%. Cl 12.6% and H 0 3.5% to be in ethanol greater than 50 weight percent (weight to weight basis) and in water also greater than 50 weight percent (same basis).

The effect of the addition of normally gaseous propellant may be observed from a consideration of the ternary diagram in the attached drawing. As will be noted, an increase in propellant from 50 to about to percent by weight of the composition reduces the solubility of the adduct from 20 percent by weight to 0 percent, and that the presence of from less than 0.5 percent water to about 1.5 percent water in the compo sition has little effect on adduct solubility.

Accordingly, by the addition of propellant to the ethanol the adduct may be precipitated therefrom, at least to the extent of having less than 0.05 part by weight of dissolved adduct in parts of the ethanol-propellant solution. The value of so precipitating the adduct is to make the adduct inactive in the pressurized container. The adduct when solubilized can be highly corrosive.

so there is an important commercial advantage to the package inactivity of the adduct achieved by this invention. indeed, it has been found that no special linings are required'in cans filled according to the present invention.

it will be apparent that upon release of the packaged composition the propellant returns to the gaseous state instantaneously whereupon the ethanol and adduct remaining as aerosol constituents are in proportions such that the adduct will dissolve in the alcohol and thus be active upon striking the users skin. This activity is immediate and the packaged product thus affords immediate astringency.

In addition to the astringent effect obtained and the control of in-can corrosion by virtue of the propellant ethanol system employed, the presence of the precipitated adduct has been found to ameliorate the caking problem heretofore encountered with aluminum chlorhydroxide per se present in an astringent or antiperspirant.

As indicated above, the present compositions also contain for continuing astringent effectiveness at least one-half part per 100 parts of the composition of a second astringent consisting of aluminum chlorhydroxide, above described. This compound or complex is available commercially under the same Chlorhydrol (Trademark) from Reheis Chemical Company. Aluminum chlorhydroxide is a widely used anti-perspirant material which has been packaged in forms to be activated upon delivery onto the skin and contact with moist secretion there. The difficulty with aluminum chlorhydroxide used alone has been the need to coat the powder for delivery to avoid choking flyaway when sprayed and the need to copackage substantial amounts of inert filler, e.g., silica to prevent caking of the aluminum chlorhydroxide into an undeliverable mass in the container. These problems have reduced the active ingredient content of aluminum chlorhydroxide sprays by requiring copackaging and delivery of inert powder.

An outstanding advantage accruing from the use of the present invention becomes apparent when it is realized that the presence of the propellant precipitated, alcohol soluble astringent, as above delineated, is interdispersed with the aluminum chlorhydroxide and serves to prevent agglomeration of the aluminum chlorhydroxide, in the manner of inert silica and/or dispersing oil, but at the same time, because the alcohol soluble material is itself an astringent, the delivered spray from the package according to this invention is completely active and free of inert powders which consume space and weight but lend no astringent power to the spray.

The two astringent materials are each present in at least 0.5 part per 100 parts of the composition and typically are together present in an amount up to 12 parts per 100. Preferably each astringent material is present in an amount between 3 and 4 parts by weight per 100 of the composition.

In addition to ethanol propellant, and first and second astringents, the present compositions may include conventional ingredients for specific purposes such as perfumes, bacteriostats and emollients to give a cosmetically elegant feel to the sprayed composition on the skin. For such purposes oily liquid emollients in amounts of from 0.5 to 15 parts per parts of the composition may be used. Preferably there is used from I to 5 parts of an emollient. Specific emollients are liquid fatty esters, fatty diesters and the polyalkylene oxide ethers of unsaturated fatty alcohols. Fatty acid esters may have the formula A-R in which A is a fatty acid radical containing from 12 to 18 carbon atoms and R is an alkyl group of from 3 to 18 carbon atoms which may be mono hydroxyl substituted, such as isopropyl myristate, isostearyl palmitate, isopropyl palmitate, hexadecyl isostearate, propylene glycol monooleate and butyl stearate. Suitable fatty esters of dicarboxylic acids may have the formula RA'R in which R is as above, A is a saturated dicarboxylic acid radical containing from 4 to 6 carbon atoms and R is an alkyl group which may be monohydroxyl substituted containing from 3 to 18 carbon atoms, Typically longer chain alkyl groups in these esters, e.g., above about 6 carbon atoms, are branched to retain liquidity for emollient purposes. Among the dicarboxylic acid esters useful herein are di-octyl adipate and di-hexadecyl suc cinate. Other specific emollients are the polyalkylene oxide ethers of fatty alcohols, particularly those in which the alkylene group contains from 2 to 3 carbon atoms, the fatty alcohol from 12 to 18 carbon atoms and having a molecular weight to be normally liquid, e.g., from 1,000 to 2,500, e.g., the polypropylene oxide ether of oleyl alcohol. Polypropylene oxides per se and mineral oils also may be used as emollients, if normally liquid. In general, many different oils may be used as is well known in the art of cosmetic preparationv The described composition is packaged in a conventional aerosol container comprising a pressure resistant can having a valved top crimped thereon and means for finger actuation of the valve to dispense the product through thecontainer dip tube and valve and out a spray nozzle.

In each of the following examples the product was formulated and packaged by first placing the alcohol insoluble aluminum salt in the container, crimping the valve in place and then adding a portion of the propellant, e.g., the 114 propellant. The alcohol soluble aluminum salt is then dissolved in the alcohol and the oily liquid emollient, if any, is blended in. Then under pressure, the balance of the propellant, e.g., propellant 12 is added to the alcohol solution. This mixture is added to the container through the container valve. In this manner, caking of the alcohol insoluble aluminum salt upon addition thereto of an alcohol solution of the other salt is avoided. This combining of the two quantities of propellant precipitates the alcohol soluble aluminum salt from its solution and the product is ready for shipment and use.

Typical formulations are given in the Examples, wherein all parts and percentages are by weight.

Aluminum chlorhydroxide (l) Aluminum chlorhydroxide-propylene glycol adduct (2) lsopropyl myristatc Ethanol Freon l2/l l4 (40/60 ratio) Aluminum chlorhydroxide Aluminum chlorhydroxitle-propylene glycol adduct Continued g z, l2/l9 Example 2 Freon 12/114 (40/60 ratio) uz,l2/l9 Example 4 Aluminum chlorhydroxide Aluminum chlorhydroxide-propylene glycol adduct Ethanol uz,29/32 Parts per I Parts 62.0 uz.29/4l Parts per 100 Parts 5.5 4.0 l6.0 69.0 uz,29/4l Parts per 100 Parts Freon l2/ll4 (1) Sold under Trademark =Chlorhydrol" and understood to he a /6 basic aluminum chlorhydroxide complex of the formula lAl, (OH l, Cl],,. Other specifications are given in U.S.P. LZXKJIXI. Example ll;

alcohol insoluble.

(2) Sold under Trademark "Rehydrol" as aluminum chlorhydroxidepropylcne glycol complex; analysis shows M 0 3694 min.; chloride l2.5 min.; AlzCl atomic ratio LJrl to Zzl; Water 7'/: max.; pH [30% \t/u in 5.0. 40 Anhydrous Alcohol) 2.5 min.: pH (309; \\-/w Water) 4.0 min.; Sulfate (S0,) 0.0571 max; Iron (Fe) l50 ppm. max.; Heavy metals (Phi ppm. max; Arsenic 2 ppm. max.: further described in U.S.P.

All of the above provide a dual action antiperspirant having immediate effectiveness as the propellant volatilizes and the aluminum chlorhydroxide-propylene glycol adduct dissolves in the ethanol, and continuing effectiveness as the aluminum chlorhydroxide is contacted with body moisture and becomes ionic and active.

EXAMPLE 5 and selected from the group consisting of dichlorodifluoromethane, dichlorotetrafluoroethane, pentafluoromonochloroethane, octafluoropropane. cyclic hexafluorodichlorobutane, propane, butane, isobutane, and pentane and mixtures thereof, at least 0.5 part of a first astringent soluble and highly astringent in alcohol but insoluble in said ethanolpropellant solution, said first astringent consisting of aluminum chlorhydroxide-propylene glycol adduct, at least 0.5 part of a second astringent soluble and highly astrin gent in water solution but insoluble in ethanol, said second astringent consisting of aluminum chlorhydroxide. the sum of said first and second astringents in said composition being between 1 and 12 parts to make up said 100 parts by weight, to effect upon dispensing of the composition from the container alcohol solution and activationof the first astringent as the propellant volatilizes for immediate astringent effectiveness and to effect water solution and activation of the second astrin- Consideration of the foregoing Table 1 reveals that in an alcohol containing system E, both astringent materials remain redispersible without the conjoint presence of silica or emollient, demonstrating that higher concentrations of astringent materials are obtainable in the present invention without caking. In (D) the absence of adduct permitted caking in a formulation despite the presence of both silica and emollient in the presence of 15 percent alcohol. The nonalcoholic formulations (A), (B) and (C) remained dispersible when both silica and emollient were used as dispersing aids.

I claim:

1. Aerosol astringent package comprising a pressure resistant container having a dispensing means and under pressure therein an astringent composition providing both immediate and continuing astringent effectiveness when applied, said composition per 100 parts by weight consisting essentially of a solution of from l0 to 20 parts of ethanol and from 60 to 85 parts of a normally gaseous liquefied propellant per part of ethanol said propellant being resistant to water decomposition gent in the applied condition as the ethanol evaporates and the second astringent is contacted with body moisture for continuing astringent effectiveness.

2. Aerosol package according to claim I in which said astringents together are present in an amount up to 8 parts with at least 1 part of each of said first and second astringents.

3. Aerosol package according to claim 2 in which there are present from 4 to 12 parts of the propellant per part of ethanol, by weight.

4. Aerosol package according to claim 3 in which said first and second astringents are each present in an amount between 3 and 4 parts by weight.

5. Aerosol package according to claim 4 in which said propellant is selected from dichlorotetrafluoroethane and dichlorodifluoromethane and mixtures thereof.

6. Aerosol package according to claim 5 in which said ethanol-propellant solution contains less than 0.05 part of dissolved astringent. 

2. Aerosol package according to claim 1 in which said astringents together are present in an amount up to 8 parts with at least 1 part of each of said first and second astringents.
 3. Aerosol package according to claim 2 in which there are present from 4 to 12 parts of the propellant per part of ethanol, by weight.
 4. Aerosol package according to claim 3 in which said first and second astringents are each present in an amount between 3 and 4 parts by weight.
 5. Aerosol package according to claim 4 in which said propellant is selected from dichlorotetrafluoroethane and dichlorodifluoromethane and mixtures thereof.
 6. Aerosol package according to claiM 5 in which said ethanol-propellant solution contains less than 0.05 part of dissolved astringent. 